Polyamide resin-dye compositions and methods of making the same

ABSTRACT

A RESIN-DYE COMPLEX FOR TOPICAL APPLICATION TO HUMAN AND NON-HUMAN KERATINOUS MATERIALS AND SYNTHETIC FIBERS, SAID COMPLEX BEING MADE OF A POLYAMIDE-POLYAMINE COMPOUND REACTED WITH A HEAT-REACTIVE PHENOLIC MATERIAL HAVING APPRECIABLE ALCOHOL SOLUBILITY, SAID RESULTING RESIN BEING COMPLEXED WITH A DYE.

United States Patent US. Cl. 260-14 8 Claims ABSTRACT OF THE DISCLOSUREA resin-dye complex for topical application to human and non-humankeratinous materials and synthetic fibers, said complex being made of apolyamide-polyamine compound reacted with a heat-reactive phenolicmaterial having appreciable alcohol solubility, said resulting resinbeing complexed with a dye.

This is a division of application Ser. No. 95,895, filed Dec. 7, 1970and now Pat. No. 3,743,622.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to resin-dyes and, more particularly, to novel resin-dyecompositions which are flexible and soluble in secondary butylalcohol-water mixture and which are useful for application to human hairor other fibers and fabrics in the form of a colored film which hascharacteristics of firm adherence, resistance to abrasion and washingwith soap and the like, and with methods for producing saidcompositions.

Description of the prior art Earlier attempts to color hair byovercoating used suspensions of pigments in resinous vehicles, as inlacquers. When such pigment suspensions were used, the coating was sothick as to stiffen the hair and also to cement adadjoining hairtogether in clumps. Spirit soluble lacquers in which dyes weredissolved, when applied in film thicknesses thin enough to leave anatural drape and hand to the hair, never achieved depth of shade neededto give satisfactory colors, and the free dye was also often a skinirritant or poison. This type of coating also caused hair to sticktogether. Furthermore, commercial lacquers are made with solvents thatare prohibited for use on human subjects by the US. Food & DrugAdministration. Shampoo resistance was either low or the films toodiflicult to remove, and such products used for hair coloring have beenwithdrawn from the market because of these adverse eflects.

THE INVENTION The foregoing and other disadvantages and defects of priorart compositions are overcome by the provision of a novel resin-dyecomplex which comprises a polyamidepolyamine compound that issubstantially balanced in its electrical character and which is reactedwith a suitable heat-reactive phenolic material such as phenol orpolyphenol and their homologues to form a polyamide-polyamine-polyphenolresin having appreciable alcohol solubility, the resulting resin beingcomplexed with a suitable dye.

We make a resin-dye combination in which the dye is substantive to theresin, i.e., it is attached to the resin by molecular forces other thanthe ordinary valence forces 3,790,512 Patented Feb. 5, 1974 such ascovalence or ionic valence. These molecular forces are mostly hydrogenbonding and, to some extent, Van de Waals forces, both electrostatic innature, as distinct from covalence where the electrons are sharedbetween two atoms in a molecule; or from ionic valence where one or moreelectrons are attached to one part of a molecule, and which therebyleaves an equal positive charge on another part, or radical, and whichparts can be separated electrolytically.

Our combination of resin and dye can be varied in compositioncontinuously, within wide limits, whereas a valence bonded combinationvaries only in distinct integral steps.

Our combinations fall in the general category of molecular complexes,and these are stable under ordinary conditions of temperature andsolution, but are unstable at higher temperatures, but whichtemperatures are much below the decomposition temperatures of the usualcovalent types.

We have had to develop a resin that could not only hold dye firmly, butalso adhere to hair. This required the combination of molecules thatcontributed high bonding strength, plus others, that gave solubility insolvents that were non-toxic, and which had a fairly high degree ofcompatibility with water. The resulting resin-dye had to adhere sostrongly to hair that it would withstand repeated shampooing, and which,when dry, would resist abrasion losses. It had to have high colorintensity because the film is much thinner than the hair it coats. Wefind that about 20% of the weight of the resin, in metal complex dye, isadvantageous to give depth of color suificient to produce a black ordeep brown. When pigments were previously used, stiffening of the hairresulted, and this was unacceptable.

Our resin, in its final form, has a backbone that is composed of apolyamide-polyamine fraction, plus phenol or polyphenol fractions, andmay contain side chains of resorcinol-formaldehyde, and/ormethylolacrylamide, added for increased solubility and for increasedbonding strength.

Ordinarily, solubility in alcohol plus Water is obtained by introducingether groups and amine groups into the backbone of thepolyamide-polyamine. However, we find that both the ether and the aminegroups neutralize the bonding power of the phenolic hydroxy groups whenpresent alone. We have found that they can be balanced against eachother so as to provide solubility without interfering with the bondingstrength. One way in which this is done is by proportioning thepolyamines, in which the secondary or tertiary amine group remains free,so that approximately 1-1.5 amine groups are present for every ethergroup. (Polyglycoldiamine has two ether groups, and polyethyleneglycoldiamine 221 has 3.7 ether groups).

Although hydrogen bonding is possessed by every molecule in which ahydrogen atom is attached to an oxygen or nitrogen atom, the degree ofbonding power varies over wide limits. When an electro-negative groupsuch as nitro, ether, or a carbonyl group is present, hydrogen that isconnected to an oxygen or nitrogen atom in an adjoining molecule willbond with it. Phenolic OH groups possess outstanding hydrogen bondingpower when alone, and this power is strengthened by negative atoms, suchas chlorine, in the same benzene ring, whereas it is weakened when thesubstituent is an electro-positive group such as primary, secondary, ortertiary amines. Nitro groups are negative, but while they increase thebonding strength of the phenolic OH group, they also bond to it and cancompletely neutralize its strength. This is true Whether the nitro groupis in another molecule in the same solvent system, or on the samebenzene ring. It therefore becomes advantageous to bring into properrelationship all these factors to achieve the foregoing desired results.This is accomplished by introducing suflicient amine groups, which areelectropositive, into the polyamide'polyamine chain to at leastneutralize or exceed the negative groups such as ether or nitro groups.

We have further found that the long chain dibasic and amino acids usedin formulating our polyamidepolyamines contribute to their solubility insecondary butyl alcohol, together With quickest solvent release ondrying. We therefore use acids containing six (6) or more carbon atomsin a line.

The phenolic resin fraction is composed of commercially available shortchain phenolic resins that have molecular weights under 1,000, areheat-reactive, and are predominantly dimethylol derivatives. Theseresins usually carry alkyl side chains attached to the benzene ring. Wefind that those resins that have side chains of six (6) or more carbonatoms give best shampoo resistance, without decrease in dye bondingcapacity. The reactive methylol group can combine directly with thehydrogen of an amine groupusually a terminal groupand may also becombined with the amide hydrogen of methylolacrylamide.

111 the case of methylolacrylamide, the double bond, being in aconjugate system, is reactive, and readily adds on to the amine hydrogenof a polyamide-polyamine, again usually on the terminal amine group.This gives a chain of polyamide-polyamine-polyphenol groups. In oneexample, we use a ratio of five (5) molecules of the polyamide-polyamineto three (3) polyphenol molecules to produce a final product having amolecular weight of around 30,000. Other suitable ratios may also beused.

This resin alone, namely, polyamide-polyamine-polyphenol, while it hasmany points at which hydrogen bonding can occur, may not possess bondingpower sutficient to meet our requirements since some of the 1:2 metalcomplex dyes muzzle much of this bonding power when used in 20%concentration, calculated on the weight of the resin. We find thatmethylol resorcinol, or formaldehyde resorcinol, adds considerably tosolubility of the final resin-dye and that 6-8 additional molecules ofmethylolacrylamide gives added bonding power and resulting greatershampoo and abrasion resistance of the film on the hair.

Hence, it is clear that if a resin of said composition is to serve forbonding both the dye and the hair, it must have a suflicient number ofbonding groups in excess of those groups which are internally bonded asbetween other and phenolic hydroxy groups, and between amine andphenolic hydroxy groups so as to bond firmly onto the hair, and that theentire composition of resin-dye have suitable or adequate solubilitycharacteristics for satisfactory or desirable color intensity whensolubilized or dispersed in a solvent system of secondary alcohol andwater containing thickening and rinsing aids such as noted in ourformulations described hereinafter.

This invention consists of a process for producing transparent coloredcoating for hair in which the dye is so firmly bound to a resin, i.e.,so strongly substantive, that the dye does not migrate into the hair, incontrast to the usual method of coloring hair. The product of ourprocess is so strongly adherent to hair that it resists both normalstrength shampoos and abrasion, but is only weakly adherent to skin andcan be removed from skin with soap and water. Color intensity is so highthat a layer whose thickness is of the order of .0001 to .0005 inch willgive deep shades-even black-on very light gray hair while leaving thehair with a natural drape and soft hand.

Substantivity, in dyestuffs, is attributed to a combination of hydrogenbonding and Van der Waals forces,

both electrostatic in nature, and is distinct from the usual ionic orcovalent type of bonding. The hydrogen bond is known to be much strongerthan the Van der Waals force, but is Weaker than a covalent or ionicbond. We have found that when dyes are covalently bonded to a resin,color intensity suffers, apparently because of interference withresonance. On the other hand, hydrogen bonding gives full color values.We have found that when a polyamide having strong hydrogen bonding to adye is used, the color value obtained by such a combination is greaterthan when the polyamide has dye side chains aifixed by covalence.

Since resins, synthetic or natural, that are composed of polarcompounds-especially when they contain hydrogen that is connected tonitrogen or oxygen-all have some hydrogen bonding capability, it followsthat they will also have a certain degree of dye-bonding capacity forproperly chosen dyes. However, the bond to hair is also due to hydrogenbonding, and all commercial resins-polyamide, polyester, etc.-whencombined with enough dye in equal film thickness to give even moderatedepths of color, lose their bond to hair and are readily removed byshampooing. Furthermore, no resin dye that has been made by us fromcommercial polyamides or from formulations given in the literature, hasbeen found to be able to carry enough dye to meet requirements of depthof shade, solubility, hair adhesion, drape, abrasion and shampooresistance, removability and product stability.

We have found that in all cases where a dye is substantive to a resin,that a molecular complex is formed whose solubility is often differentfrom either that of the dye or of the resin. We have further found thatwhile a sulfonated dye may be substantive to the resin, and form astrong hold to it, the entire resin-dye compound is removable from hairby shampooing-the bond to hair being weaker than the solubilizing actionof the sodium salt of the sulfonic acid radical, when soap is present inthe shampoo.

In order to achieve improved shampoo resistance, we have, therefore,employed unsulfonated dyes-preferably the 1:2 metal complexes (1 metalatom:2 dye molecules). Our resin-dyes, in contrast to previouscommercial hair dyes, particularly the permanent paraphenylene diaminetypes, while essentially permanent and resistant to normal concentrationof commonly .used shampoos, are readily removable from the surface ofthe hair by supplementing such conventional cationic, anionic, ornon-ionic shampoos with a sulficient amount of an organic solvent suchas a glycol-ether or the like. This is not possible with the commercialpermanent hair dyes previously on the market which are required to, anddo, penetrate the hair shaft for purposes of coloration.

What we have done, therefore, is to develop a process and formulationwhich, while bearing certain similarities to the prior art shown, areessentially different in the choice of components, and in the way theyare combined to produce an end product which has the desired properties,and which differ fundamentally from all other combinations ofresin-l-dye or pigment+resin, where commercially existent or indicatedin any of the patents investigated. Many combinations of dye with resinthat earlier patents have described, use covalent bonding of dye toresin; they difiere from each other in the nature of the bond--whetherit is an ester, amide, ether, or other like linkage.

Others, like Jacobson (US. Pat. 3,268,461, Aug. 23, 1966), grindpigments into a polyamide vehicle to make inks, in which instanceswetting, adsorption, and absorption are involved.

Our films are of the order of .0001 to .0003 inch thick. This isessential because films that are as thick as, or thicker than thediameter of the hair being coated, stiffen the hair and interfere withthe natural drape and feel. The requirement of minimal thickness of filmrules out pig ment suspensions as in paints and lacquers.

It is also well known in the art of formulating inks that acidic resinssuch as shellac, for example, must never be used with a basic pigmentsuch as zinc oxide or with a basic dye, because gels result thatinterfere with ink flow.

Our resins, on the other hand, are so formulated that most of thepreviously mentioned shortcomings are avoided, and by making the dyesubstantive to the resin a unitary resin-dye complex is obtained inwhich neither dye nor resin acts independently when in solution insecondary butyl alcohol and Water, and which possesses, additionally,stronger bonding power to hair than to itself, so that films onadjoining hair do not cement together. In some cases, for non-humanapplication, any partially water-miscible alcohols might be used if theyare suitable for the purpose of coloring natural or synthetic fiberssuch as are utilized in wigs, furs, fabrics, and the like.

For human use, drying must be by evaporation at temperatures employed inhair dryersabout 45 C. to 50 C.to bring application time intopracticable limits.

As our resin-dyes are apparently molecular complexes in which thebonding forces involved are mainly hydrogen bonding, Van der Waalsforces, or similar electrostatic forces, other than covalence or ionicvalence, their composition can be varied continuously within widelimits. We have made these compounds with from less than 1% to as muchas 60% of dye, calculated on the weight of the resin used. For practicalpurposes, less than dye may have too little color intensity, while morethan 30% might introduce solubility problems when secondary butylalcohol, with or without water, is the solvent. In all concentrations,however, the resin-dye acts as a unit. No free dye exists in ourcombinations and, therefore, no dye can diffuse into the hair shaft.

In order to resist abrasion and normal concentrations of shampoo, thisproduct must adhere firmly to the substrate, e.g., hair, and weaccomplish this by having excess hydrogen bonding capacity beyond thatneeded to hold the dye, built into the resin. In addition, the film musthave sufiicient cohesion so that the outermost molecules of the film donot rub oif.

Examples follow in which two types of resin are produced. Our polyamidesare of two general types: (1) polyamide-polyamine-polyphenol in whichthe methylol polyphenol is directly attached to the polyamine fraction,and (2) where the methylol groups of the polyphenol fraction are firstreacted with a methylol amide that contains a conjugate double bondwhich subsequently opens up to react with an amine group of thepolyamide-polyamine fraction.

Since it has been our experience that a multiplicity of phenol groupsgive best bonding power for resin to dye and resin-dye to hair, we havefound it necessary to design a type of resin that gives the solubilityof the polyamide-polyamine resin with the bonding power of the phenol,uninterfered with by the solubilizing chemical groups such as aminewhich are usually present, and ether groups which may be present. Thishas been accomplished by making low molecular weight polyamide-polyaminecompounds and causing them to react with low molecular weight phenolicresins tha have active methylol groups and/or conjugated double bonds.These short chain polyamide-polyamines are made by reacting dibasicacidsand optionally, amino acids or lactamswith aliphatic diamines andtriamines.

The following are typical examples for making our low molecular weightpolyamide-polyamine resins.

EXAMPLE I Molecular Weights EXAMPLE II Molecular weights 1 moleculeaminoundecanoic acid 201 4 molecules xylylenediamine 544 3 moleculesdiethylene triamine 309 4 molecules polypropyleneglycoldiamine 190(Jefferson Chemical Co.) 760 7 molecules dodecanedioic acid 1610 3molecules dimer acid 1800 The mixture was heated at C.-220 C. for fivehours. Reaction began at 145 C.147 C. H O evolution Was at peak at C. Nofurther H O evolution was observed above 205 C. Final temperatures werefrom about 210 C. to 230 C. Titration showed five amine groups twoterminal primary amine groups and three secondary amine groupsfor thetheoretical Weight of 4990.

EXAMPLE 111 Molecular weights 3 molecules diethylene triamine 309 2molecules polypropyleneglycoldiamine 230 (Jefferson Chemical) 460 3molecules Laromin C (cycloalkane diamine) (B.A.S.F.) 720 2 moleculesdimer acid 1200 5 molecules dodecanedioic acid 1150 2 moleculescaprolactam 226 Laromin C is a mixture of cycloalkane diamines of thetype di-(methylcyclohexyl) diamine.

The above mixture was heated for five and one-half hours, from 140 C. to215 C. Reaction commenced at 140 C.-142 C., and visible evolution ofvapors ceased at about 200 C. Titration indicated 5.1 amine groups whencalculated for the theoretical molecular weight of 3813.

Approximately 5% by weight excess of triamine in the foregoing ExamplesI, II and III, is used to compensate for losses occurring throughvolatilization with the steam generated by the reactions.

These short chain polyamides-polyamines are combined directly orindirectly with low molecular weight phenolic resins that have severalunreacted methylol groups. They are commercially available as CKM-l734and CRM- 0803 from Union Carbide Corporation; Durite SK 798- 74 ofBorden Company, and Amberol ST-137 of Rohm & Haas. The CKM-1734 andCRM-0803 have approximate molecular weights of 700, while Durite SD798-74 has an approximate molecular weight of 400. All are heat reactiveand contain 3 to 4 phenol radicals and all, except the Durite, are madefrom alkyl phenols. We have found that those made with the longer alkylgroups, having at least four carbon atoms, as in CRM-0803, give betterdetergent resistance than do those with shorter chain alkyl radicals.

The phenolic resin may be combined with the polyamide-polyamine eitherdirectly, by reaction of its methylol groups with the amine groups ofthe polyamide as shown in the following Method I, and which produces aproduct that is soluble in secondary butyl alcohol plus water, orindirectly by first reacting the methylol groups of the polyphenol withN-methylolacrylamide, as in Method H.

The latter reaction is conducted under mildly acidicconditions-approximately pH 3 to pH 5in order to catalyze the reactionof the methylol-amide condensation and to prevent the opening of thedouble bond.

Polyamide-polyamine Unit of final resin R is balance ofpolyamide-polyamine.

R is H or any hydrocarbon radical.

In the following Method II, the process comprises a first step ofcombining a heat-reactive polyphenol with a methylol amide havingconjugated double bonds such as N-methylol acrylamide, N-methylolcrotonamide, or N- methylol methacrylamide. In the second step, theproduct of the first step is reacted with a polyamide-polyamine to forma resin which can be used directly, or further modified to produce theresin-dye complexes herein.

METHOD II STEP I R R R H H E) H H H H (::=d-o-N-H OH+ b E b-H H H(|-H HH H H 1 OH 011 on on Metlllyloild Heat reactive polyphenol acryam e H HHN( l=l H- H H Methylol acrylamide R B. R

H H O H H H H O H H 6 it 6 ti N- o I oN- -c= H H-h-Hn H H HH- -11 I 011OH on A 2112 R is H or any hydrocarbon radical. X is polyphenol methylelaerylannde.

STEP H H H H H H R H H I 5 E I v I I I N- F.-|N X II'R-(l3-1?T H H H H HR H H Pol amide- Polyamidep lgamine polyamine H H H O H H 0 H H H H I II 1 l, I I R-C-N- N-|X-]- |]-N;-R H H H H HH HHC|3H H H HPolyamide-polyamine-polyphenol resin where R is the balance of thepolyamide-polyamiue molecule.

We now have a series of polyphenol radicals connected at each endwith apolyamide-polyamine. We have found a satisfactory combination forsolubility and for bonding power to dye, and to hair, to be the reactionproduct of 7 to 10 molecules of polyamide-polyamine with 5-9 moleculesof the polyphenol as in Method I. In Method II, the polyphenol isreplaced by 5 to 9 molecules of the reaction product of polyp-henol andmethylolacrylamide, assuming the reaction product to have a molecularweight of 900. By the introduction of phenolic groups into thepolyamide-polyamine chain, resulting in a polyamidepolyamine-polyphenolthere is achieved a considerable degree of bonding power. Optionally, inorder further to enhance both the solubility and the bonding power ofthe polyamide-polyamine-polyphenol, step (a) and (b) may be followed:

(a) Adding 2-8 molecules of the formaldehyde adduct of adihydroxybenzene such as catechol, resorcinol, hydroquinone or theirhomologues, which is made in approximately 1:1 molecular ratio ofresorcinol to formaldehyde, for example. This is made from 1 molecule ofresorc'mol plus 1 of formaldehyde, in secondary butyl alcohol and atapproximately 10% concentration, using 1% acetic acid as catalyst andallowing the solution to stand at room temperature for approximately 48hours. The mixture of resorcinol-formaldehyde with thepolyamide-polyarnine-polyphenol methylolacrylamide is then refluxed forfrom 2-3 hours at a pH of 8-10. (b) 1-10 molecules of methylolacrylamidemay then be added to the above described solution and again refluxed for2-3 hours.

The resorcinol-formaldehyde has been found to increase solubility of theresin-dye and stability of the solutions in secondary butyl alcohol. Themethylol acrylamide adds to the bonding power of the resin-dye and givesit greater shampoo resistance. It is not known just how theresorcinol-formaldehyde attaches to the resin, since it may react withthe hydrogen of an amine or amide group, or with a phenol, all of whichare present. The methylolacrylamide most probably reacts with primary orsecondary amines by opening of the double bond to form secondary ortertiary amines at the backbone. This resin solution, which has had a pHof 8-10 up to this point, is now made acid to pH 3.5-5.0 with aceticacid, and then the dye, in an amount equal to 12%30% of the weight ofthe resin, is added.

We have found it most convenient to make a 5% solution of the dye in themonomethyl ether of propylene glycol, although any other good slventthat is also water soluble may be used. This resin-dye solution isallowed to stand from 5 to 10 minutes at 75 -90 C., to reachequilibrium, following which it is cooled to 40 C. or lower, and thenpoured into suflicient cold water+NH OH or other mild alkali toprecipitate it at a final pH of about 6.5 to 8. A coagulant, usuallyammonium thiocyanate, may be added. A soluble thiosulfate, or sodiumchloride, also may be used but require higher concentrations to beequally effective. The precipitated product is Washed free of salt andde-watered. It is then dissolved in secondary butyl alcohol with about10%-30% water, to a concentration of approximately 5%-6%. This solutionis now the basis for the final product, which is varied in compositionto meet various requirements such as solubility of resin-dye made fromdiiferent dyes and different drying times.

The manner of making the final resin-dye products is described in thefollowing examples.

9 EXAMPLE IV Part (A): Grams resin-dye solution in secondary butylalcohol and 10%-30% water, containing Irgacet Black RL (of wt. of resin)100 Parts (A) and (B) are mixed together with thorough agitation andallowed to stand at room temperature for at least 24 hours, since aninitial metastable equilibrium slowly converts to the final form in thattime. A clear dispersion-solution results which, on evaporating on hair,leaves a continuous, strongly adherent and glossy film of high colorintensity that can be rinsed with cold water immediately after applyingand, if desired, can be sham pooed without loss of color when dry. Thehigh boiling solvents as in Example IV and in the following Example V,are added in small quantity and have been found desirable in many casesfor producing a smooth film.

EXAMPLE V Part (A): Grams 5% resin-dye solution in secondary butylalcohol and 10% to 25% water, containing Spirit Soluble Brown BE(B.A.S.F. Co.)

(20% wt. of resin) 100 Mix as directed in Example IV. These preparationsof Examples IV and V exhibit comparatively low viscosity characteristicsand must be used with a suitable applicator.

Although several types of dyes may be used, we have chosen the 1:2 metalcomplex dyes, preferably the azo types, because they have been shown toform the most suitable resin-dyes for our purposes from the standpointof firmness of combination with the resins, high color intensity, goodstability of the solution-emulsions, and very low fat solubility andtoxicity. These molecules are also much larger than those of thenon-metalized dyes and this, together with their negligible fatsolubility, renders them practically incapable of penetrating into thepores and of being absorbed in the blood stream.

While many of the 1:2 metal complex dyes may be added directly to theresin solution, we find that some, especially the blacks and to a lesserextent the browns, tend to cross-link with the resin if the latter hasfree primary or secondary amine groups, and this is most pronounced whenthere are no phenolic groups in the backbone. These cross-linkedproducts vary widely in solubility in secondary butyl-alcohol pluswater, but the blacks, especially, form products that are only sparinglysoluble 10 in the secondary butyl alcohol plus water, and leave thesupernatant liquid with only low color intensity.

We have found that this cross-linking can be kept within acceptablelimits if the dye is first mixed, in solution, with approximately onemolecule of methyl ethyl ketone, acetyl acetone or an alkylacetoacetate, a dialkyl itaconate, or an alkyl or hydroxyalkylmethacrylate, for each molecule of dye.

The following are typical examples of 1:2 metal dyes listed in theColour Index (C.I.):

Listed as Color: Zapon Black BE (BASF) C.I. #12195. Zapon Fast Brown BE(BASF) Solvent Brown 37.

Zapon Fast Yellow 3RE (BASF) Solvent Orange 45 and CI. #11700.

Zapon Fast Red GE (BASF) Solvent Red and Orasol Brown 5R (Ciba) SolventBrown Orasol Black BV (Ciba) Solvent Black #6.

Irgacet Black RL (Geigy) Solvent Black #29.

Irgacet Brown 2RL (Geigy) Solvent Brown We-find that basic dyes such asBismark Brown, for example, form weaker combinations with ourpolyamidepolyamine-polyphenolic resins but give good color coating onhair. However, this type of resin-dye has relatively poor shampooresistance and when stripped from the hair, leaves some free dye toenter the hair and to stain the skin.

Phenolic dyes, such as alizarin, form firm combinations with basicresins. Thus, if a 5% solution of alizarin is mixed with an alcoholsolution of the resin, in the proportionof 15-20 parts dye to parts ofresin, and then precipitated in water, and redissolving the precipitatedproducts in 66/33 secondary butyl alcohol-water, a stable solutionresults whose emulsions give hair coatings with fair soap resistance.

Our resins, as now formulated, have a relatively high water tolerance insecondary butyl alcohol solution and are to a very large degreeself-emulsifying, thereby giving greater stability to the product and tothe film during the drying process with its rapid changes of compositionof solvent phase. Similarly, our resin-dyes as now formulated,preferably with 1:2 metal dyes, have a relatively high water tolerancein secondary butyl alcohol solution, contributing also to greaterstability to the product during the film-forming stage, in which thebond to the hair is established.

Earlier work had shown that emulsions made with most emulsifying agentsor protective colloids had poor bonding to hair because the emulsifierformed a barrier between hair and resin-dye.

Many of the usual thickening agents-starches, gums, etc.-do not toleratealcohol and some, such as ethyl cellulose, polyvinyl-alcohol, polyvinylpyrrolidone, interfere with the bond between resin-dye and hair.

We have discovered that ethoxylated and propoxylated polyols, whencombined either with mixed ethoxylated cellulose or with hydroxypropylcellulose, and which have both water and butyl-water solubility, servesuccessfully as colloid dispersing, thickening and protective agentswhen used in limited quantity, such as approximately 10% to 40% byweight, in the secondary butyl-water systems containing our resin-dyes,without incurring the aforementioned interferences. The viscosityefi'ect may be enhanced by the use of a diketone such as acetyl acetoneadded to the foregoing mixture in a quantity equal to between 5% to 15%of the weight of the cellulose derivative used. In order to obtainmaximum viscosities from these materials in a secondary butyl alcohol:HO system, we have used polyhydroxy phenols and esters of polyhydroxyphenolic acids, as later shown, which serve to 1 1 increase theviscosity thereof markedly. It is noteworthy that these polymers shouldbe maintained in suitable balance of secondary butylzH o compositions tothat employed for resin-dye solution, so as to make for a homogenoussolution-dispersion.

The viscosity of our resin-dye preparation may be varied within widelimits to suit various methods of application. If the method ofapplication requires deposition of the fluid on the hair and thenspreading it with comb or fingers, a higher viscosity is needed toprevent dripping and a suitable thickener is incorporated for thatpurpose.

The thickening effect may be varied by changing the concentration of theindividual ingredients, and it may be considerably increased by theaddition of those agents that have strong hydrogen bonding properties ontwo or more groups in a molecule, to effect a crosslinkage. We havefound phloroglucinol and pyrogallol, as well as the esters ofpolyhydroxy phenolic acids, such as those of gallic acid, to be veryeffective. We also find this effect to be produced by diketones such asacetylacetone, and by esters of keto acids such as ethylacetoacetate. Wehave discovered that the ethoxylated-propoxylated polyols greatlydecrease the adhesion of the resin-dye to the skin, thereby making itsremoval from the skin easier.

THICKENER EXAMPLE I To 95 grams cold water, in a blender or high speedmixer, add 0.5 gram phloroglucinol (or resorcinol, catechoi, etc.). Whendissolved, add slowly 5.0 grams Klucel H (Hercules, Inc.). Mixthoroughly. Add 250 grams secondary butyl alcohol containing 20 gramsPluronic P-l04 (Wyandotte Chemical Co.). Stir at high speed until thereare no lumps of gel.

THICKENER EXAMPLE II To 95 grams water in a blender, add

250 grams secondary butylalcohol 50 grams P-104 (anethoxy-propoxypolyol) 5 grams acetoylacetone.

Mix thoroughly, and when uniform, add 5 grams Klucel H slowly(hydroxypropyl cellulose). Stir until no lumps remain.

THICKENER EXAMPLE 1H 95 grams water 250 grams secondary butyl alcohol 20grams Pluronic P-l04 (an ethoxy propoxypolyol) 20 grams Pluronic L-lOl(an ethoxy propoxypolyol) 5 grams acetylacetone.

Mix thoroughly and add slowly 5 grams Klucel H. Stir until uniform.

While the foregoing procedures give good depth of color, filmcontinuity, drape, abrasion and shampoo resistance, they leave the hairwith somewhat drier feel than it possessed originally. This dryness maybe counteracted in two ways: (1) by subsequent application of a shampoocontaining emulsified Wax or fatty substances, or (2) by incorporationinto the mixture of a dispersible additive that leaves a slipverydeposit upon the surface of the resindye film. We have called theseadditives silkifiers. In the latter instance, these compounds must bedispersed within the thickener mixture, which acts as protectivecolloid, in order to minimize interference with bonding of resin-dye tohair. Good results have been obtained by using amides of saturated fattyacids that contain 18 or more carbon atoms, together with highlypropoxylated polyols, such as Pluronic L101 as part of the thickener.Ceresin, car-nauba, zinc stearate and petrolatum may also be used.

The foregoing indicates the desirability of compounds that containstrongly polar groups that can be bonded by hydrogen bonds or Van derWaals forces sufiiciently stronger to become an integral part of thethickener.

An example of the finished product is as follows: To 25 1 grams ofthickener No. HI, add 5-15 grams of 2% fatty acid amide such asarachidyl-behenyl amide, which acts as a silkifier, in hot secondarybutyl alcohol. Mix thoroughly, and when cold, add, premixed, grams 5%-6% resin-dye complex in 88%12% secondary butyl alcohol plus water plus0.3 gram glaciala cetic acid, plus 0.6 gram monomethylcther of propyleneglycol, plus 5.0 grams ace tone. Mix thoroughly until a uniform andstable system results. This is now ready to apply to hair.

We have now achievel a homogenous solution-dispersion system suitablefor application to hair in a manner so as to provide a continuous colorfilm thereon and having sufiicient density of color through anintegration of prop erties. The design of the resin and process forproducing it must provide the necessary solubility together with therequired hydrogen bonding properties in order that when the dye has beenadded, the resulting resin-dye complex is compatible with thebutyl-alcohol Water solution of the polymers used for both thickeningand emulsification and that the resin-dye plus thickener does notinterfere with the bond, to hair, nor with the continuity of theresin-dye film.

Although the present invention has been described with reference toparticular methods and examples, it will be apparent to those skilled inthe art that variations and modifications can be substituted thereforwithout departing from the principles and true spirit of the invention.The abstract given above is for the convenience of technical searchersand is not to be used for interpreting the scope of the invention andclaims.

What is claimed is:

1. A resin-dye complex comprising the reaction product of apolyamide-polyamine compound having a quantity of groups that are ofelectropositive character in an amount of at least electrically equal toor greater than the groups therein that are of electronegativecharacter, and of a heat-reactive phenolic material to form apolyamidepolyamine-polyphenol resin having substantial solubility insecondary butyl alcohol plus Water, the latter resin then beingcomplexed with an unsulfonated dye to form a product having adequatesolubility in secondary butyl alcohol plus water and having strongexternal bonding power, said polyamide-polyamine compound being thereaction product of lactarns or amino acids or dibasic acids or mixturesthereof having six or more carbon atoms in a line, with diamines ortriamines or mixtures thereof, said heat-reactive phenolic materialhaving alkyl side chains, said resin dye complex being dissolved anddispersed in a partially water soluble alcohol plus water, said solutionand dispersion containing thickening materials comprising polymershaving ethylene and propylene oxide components together with cellulosederivatives containing either hydroxypropyl and/ or hydroxyethylcomponents, plus a complexing agent taken from the group consisting ofphloroglucinol, pyrogallol, propyl gallate, resorcinol, acetyl acetoneand ethyl acetoacetate, said thickening materials being soluble insecondary butyl alcohol plus water.

2. A resin-dye complex according to claim 1 in which the thickeningagent further includes one or more silkifying agents selected from thegroup consisting of amides of aliphatic acids containing at leastsixteen carbon atoms, zinc stearate, carnauba wax, ceresin, andpetrolatum.

3. A resin-dye complex comprising the reaction product of apolyamide-polyamine compound in which the electropositive groups are atleast electrically equal to or greater than the electronegative groupstherein, and of a heat-reactive polyphenol material, said reactionproduct then being further reacted with, first, aformaldehydedihydroxybenzene adduct, then with an N-methylol amidehaving conjugated double bonds, and finally complexing the resultingcompound with an unsulfonated dye to form a product having substantialsolubility in secondary butyl alcohol plus water and having strongexternal hydrogen bonding power, said polyamide-polyamine compound beingthe reaction product of lactams or amino acids or dibasic acids ormixtures thereof having six or more carbon atoms in a line, withdiamines or triamines or mixtures thereof, said heat-reactive phenolicmaterial having alkyl side chains, said resin dye complex beingdissolved and dispersed in a partially water soluble alcohol plus water,said solution and dispersion containing thickening materials comprisingpolymers having ethylene and propylene oxide components together withcellulose derivatives containing either hydroxypropyl and/orhydroxyethyl components, plus a complexing agent taken from the groupconsisting of phloroglucinol, pyrogallol, propyl gallate, resorcinol,acetyl acetone and ethyl acetoacetate, said thickening materials beingsoluble in secondary butyl alcohol plus water.

4. A resin-dye complex according to claim 3 in which the thickeningagent further includes one or more silkifying agents selected from thegroup consisting of amides of aliphatic acids containing at leastsixteen carbon atoms, zinc stearate, carnauba wax, ceresin andpetrolatum.

5. A resin-dye complex comprising the reaction prodnet of apolyamide-polyamine compound in which the electropositive groups are atleast electrically equal to or greater than the electronegative groupstherein, and of a heat-reactive phenolic material that has beenpreliminarily combined with a methylol amide having conjugated doublebonds, and finally complexing the resulting compound with anunsulfonated dye to form a product having adequate solubility insecondary butyl alcohol plus water, and having strong external hydrogenbonding power, said polyamide-polyamine compound being the reactionproduct of lactams or amino acids or dibasic acids or mixtures thereofhaving six or more carbon atoms in a line, with diamines or triamines ormixtures thereof, said heat-reactive phenolic material having alkyl sidechains, said resindye complex being dissolved and dispersed in apartially watersoluble alcohol plus water, said solution and dispersioncontaining thickening materials comprising polymers having ethylene andpropylene oxide components together with cellulose derivativescontaining either hydroxypropyl and/or hydroxyethyl components, plus acomplexing agent taken from the group consisting of phloroglucinol,pyrogallol, propyl gallate, resorcinol, acetyl acetone and ethylacetoacetate, said thickening materials being soluble in secondary butylalcohol plus water.

6. A resin-dye complex according to claim 5 in which the thickeningagent further includes one or more silkifying agents selected from thegroup consisting of amides of aliphatic acids containing at leastsixteen carbon atoms, zinc stearate, carnauba wax, ceresin, andpetrolatum.

7. A resin-dye complex comprising the reaction product of apolyamide-polyamine compound in which the electropositive groups are atleast electrically equal to or greater than the electronegative groupstherein, and of a heat-reactive phenolic material that has beenpreliminarily combined with an N-methylol amide having conjugated doublebonds, said reaction product being further reacted with, first, aformaldehyde-dihydroxybenzene adduct, then with an N-methylol amidehaving conjugated double bonds, and finally complexing the resultingcompound with an unsulfonated dye to form a product having adequatesolubility in secondary butyl alcohol plus water, and having strongexternal hydrogen bonding power, said polyamide-polyamine compound beingthe reaction product of lactams or amino acids or dibasic acids ormixtures thereof having six or more carbon atoms in a line, withdiamines or triamines or mixtures thereof, said heat-reactive phenolicmaterial having alkyl side chains, said resin-dye complex beingdissolved and dispersed in a partially water soluble alcohol plus water,said solution and dispersion containing thickening materials comprisingpolymers having ethylene and propylene oxide components together withcellulose derivatives containing either hydroxypropyl and/ orhydroxyethyl components, plus a complexing agent taken from the groupconsisting of phloroglucinol, pyr0 gallol, propyl gallate, resorcinol,acetyl acetone and ethyl acetoacetate, said thickening materials beingsoluble in secondary butyl alcohol plus Water.

8. A resin-dye complex according to claim 7 in which the thickeningagent further includes one or more silkifying agents selected from thegroup consisting of amides of aliphatic acids containing at leastsixteen carbon atoms, zinc stearate, carnauba wax, ceresin, andpetrolatum.

References Cited UNITED STATES PATENTS 6/1971 Hewitt 810.1 8/1971Kalopissis 810.1

US. Cl. X.R.

